Condensation product of acylated



Patented Jan. 30, 1945 UNITED STATES, PATENT OFFICE 2,368,599 CONDENSATION PRODUCT OF ACYLATED HYDROXYAROMATIC ACID Orland M. Reiif, Woodbury, N. J., assignor to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York No Drawing.

Application March 12, 1942,

Serial No. 434,388

1 Claim.

This invention relates to the production of certain new chemical comp unds or compositions which may be generally designated as the sul-.

given to such compounds in which the acyl group corresponds to an oxy inorganic acid (such as phosphorous acid) In other words, the compounds of the present invention are nuclear alkyl-substituted aromatic sulfides, selenides, or tellurides characterized by the presence of an aromatic nucleus having a nuclear hydrogen replaced by an ester- (oxy-acyl) group and another nuclear hydrogen replaced by acarboxyl group. The preferred compounds of the present invention comprise those of the above general class in which the alkyl-substituent or group is a heavy alkyl group (preferably of not less than twenty carbon atoms). Another and miscible heavy alkyl-substituted or wax-substituted compositions is based upon the discovery that they are of multifunctional activity, when blended with viscous mineral oil fractions in that they efi'ect improvement of several unrelated and related properties of the oil. For example, this preferred oil-miscible group of compounds or.

compositions coming within the general field of invention contemplated herein are effective, when blended in a minor proportion with mineral oil fractions of the lubricant type, to depress the pour point, improve the viscosity index (V. 1.), and inhibit oxidation of i the oil. By inhibiting oxidation these oil-miscible compositions act to retard the formation of sludge and acidic products of oxidation. They also have a peptizing action on such sludge as may eventually *be formed. Thus, any one of these preferred oilmiscibl compounds or compositions may, for example, be used in internal combustion engine lubricants to retard or prevent the sticking of piston rings or prevent the corrosion of bearings, particularly those formed of alloy metals normally susceptible to corrosion, etc, and at the same time more specifically preferred product of the present invention comprises an intimate mixture of compounds falling within the above general class wherein the characterizing acyl and carboxyl groups and also the divalent elements mentioned above are the same and wherein the alkyl substituents in said compound are attached to the aryl nuclei and consist essentially of hydrocarbon radicals corresponding substantially to the different aliphatic hydrocarbons contained in paraflin wax. This preferred product is hereinafter referred to as a. wax-suhstituted compound (of the above general class) With respect to the above mentioned heavy alkyl-substituted or wax-substituted compounds or compositions of the present invention, further preference is given within this group to those which are soluble in 'or miscible with mineral oil.

The addition agents of the present invention are considered to be condensation products wherein two or more of the aromatic nuclei of the characterizing acyloxyaromatic carboxyl groups are presumably interconnected through a linkage (or linkages) comprised-of an element selected from the group consisting of sulfur, selenium, and tellurium preference being given to sulfur. Through the introduction of sulfur, for example, in the manner-or manners to be hereinafter described, I obtain what may be broadly termed a sulfide of an aroxy-acyl carboxylic acid. The carboxyl group may 'be attached directly to the aromatic nucleus or indirectly through an aliphatic chain although the former is the preferred type.

My preference for the above mentioned oil it will act to depress the pour point and improve the viscosity index of the oil.

It should be understood that the use of these preferred oil-miscible compounds or compositions is not confined to lubricating oils, but they may be employed in any mineral oil fractions where one or more of the improved properties recited above is desired. In this regard it is to be further understood that the present invention is not concerned with mineral oil compositions containing these preferred oil-soluble compounds, such oil compositions forming the subject matter of my copending application Serial No. 330,533, filed April 19, 1940, to which reference is made for further details in the composition of these compounds.

It is also to be understood that while our invention contemplates oil-miscible compounds or compositions of the type above referred to as adue to the presence of particular substituents such for instance as a particular acyl or residual hy droxyl group, Numerous other uses of the compositions contemplated herein will be apparent to those skilled in the art from the following description of their compositions and sy t esis.

methods of As previously pointed out the preferred compounds or compositions contemplated by this invention are characterized by the fact that at least one replaceable hydrogen on the aromatic nucleus is substituted with an aliphatic hydro-- carbon radical or group characteristic of an allphatic hydrocarbon of high molecular weight which we may term a heavy alkyl group. For obtaining' the preferred group of compounds or compositions which are miscible with mineraloil and which possess the multi-functional oil-improving properties, we have found that this "heavy alkyl substituent in the acyloxyaromatic-carboxylic acids under discussion must be derived from a predominantly straight chain aliphatic hydrocarbon of at least twenty carbon atoms such as characterize crystalline petroleum wax. As a matter of fact, petroleum wax is considered to be a preferred source of the heavy alkyl" substituent and it is for that reason that the compounds or compositions described herein are referred to as wax-substituted. It is to be understood, however, that the term wax as used herein, is applied in a broad sense and is intended to include any pure compound or mixture of compounds predominantly aliphatic in nature and containing at least twenty carbon atoms which is susceptible of attachment to an aromatic nucleus to provide a substituent which, in the proper proportions, will impart to the characterizing aroxyacylcarboxylic acid sulfide (or selenide or telluride) group or nucleus the multifunctional oil-improving properties referred to.

In the preferred group of compounds or compositions contemplated herein, which are oil-miscible and which by virtue of their heavy alkyl (wax) substituent have multifunctional properties inmineral oil blends, it is important that the with a radical selected from the group consist-' ing of: aliphatic hydrocarbon groups having less than twenty carbon atoms, hydroxyl, ester, xanthate, alkyl sulfide, aryl sulfide, keto, alkoxy, aroxy, aldehyde, oxime, aralkyl, aryl, alkaryl, halogen, nitroso, N-thio, N-acyl, cyano and (-112) formed by hydrogenation. Compounds of the above general formula-type are illustrated by the following specific formula:

.OAc A0 R x. R

in which at least one of the Rs represents an aliphatic radical or group containing at least twenty carbon atoms-and in which the remaining Rs' represent'residual hydrogen which may be replaced with a radical selected from the group consisting of: aliphatic groups containing less than twenty carbon atoms, hydroxyl, ester, xanthate, alkyl sulfide, aryl sulfide, keto, alkoxy, aroxy, aldehyde, oxime, aralkyl, aryl, alkaryl,

halogen, nitroso, N-thio, N-acyl, cyano and (-H2) formed by hydrogenation; and in which Ac represents an acyl group; and in which X represents a divalent element selected from the group consisting of sulfur, selenium and tellurium, and n represents the number of such divalent elements, from one to four or more; and in which the hexagonal ring represents a mono-, dior tri-cyclic aromatic nucleus.

It will be understood of course that where the number of divalent elements (represented by X in the above formula) is greater than one they form a chain of such elements which are interconnected among themselves.

It will also be understood that since the condensation reaction (hereinafter described) which is employed in synthesizing the sulfides, etc., contemplated herein, is presumably attended by a certain amount of multiple condensation, such further condensed compounds, herein called polymers, are'included herein within. the terms sulfides, etc., and as coming within the general formula above. The general formulae corresponding to the polymers of this character will be readily understood from the above by those skilled in the art.

It is pointed out further that the term sulfide, as used herein, is inclusive of the monosulfides, disulfides, trisulfides, tetrasulfides, etc.;

that is, it includes both monosulfides and polysulfides and the corresponding rule applies to the terms "selenide and telluride."

It will be understood that the compounds or compositions contemplated by this invention may be pure compounds satisfying the conditions enumerated above with any one of the various monoor polycyclic aromatic nuclei in the characterizing nuclear group. However, in manufacturing the preferred composition by the preferred procedure, as will appear later on', the final product obtained is normally or usually a mixture of different compounds the individual characteristics of which differ in their alkyl substituents (according to the different aliphatic hydrocarbons in an alkylating material such asparaflln wax) in the number of alkyl substituents on the characterizing nucleus and in the number of nuclei attached to a single long chain alkyl group. For further details in the composition of such mixtures of compounds reference is made to my aforesaidapplication Serial Number 330,533, filed April 19, 1940.

Asaforesaid, it is important'that the waxsubstituted compounds of the present invention which are preferred for use as oil-improving agents have the aryl nucleus substituted with heavy alkyl groups to an extent such that this heavy alkyl (wax) substituent comprises a sufficient proportion of the composition as a whole to render the same oil-miscible so that it will form a mineral oil solution or colloidal suspension which will remain stable as such under pound is used; (b) whether the aryl nucleus is monoor polycyclic or monoor polyhydric;

(c) monoor polysubstitution of the aryl nucleus with heavy alkyl groups; and (d) other substituaseaoeo 3 ents on the nucleus which may be of positive or negative or of neutral oil-solubilizing activity.

In view of the foregoing variables it would be impracticable and probably misleading to attempt to give an expression and figure which would indicate accurately the proper ratio of hydroxyaromatic constituent to the wax-substituted hydroxyaromatic constituent in the starting material which would satisfy all cases taking these variables into account. As a guide for preparing these preferred compounds, however, our research indicates that in general the ratio, expressed as weight of hydroxyaromatic component in the product to the corresponding wax-substituted hydroxyaromatic nucleus or component therein, should not be greater than about seventeen parts by weight of the former to about 100 parts by weight of the latter, or

about 17 per cent, when the hydroxyaromatic' component is expressed in terms of its chemically equivalent weight of phenol. This ratio. hereinafter designated as the phenolic ratio." does not take into account other substituents on the nucleus, but it will serve as a working guide for the preparation of these preferred compounds. A further general guide for the synthesis of these preferred compounds is to substitute the aryl nucleus with paraffin wax or derstood that the corresponding selendes and tellurides are contemplated by and come within the scope of the broad invention.

One general procedure for synthesizing the monoand polysulfides of the acylated alkylsubstituted hydroxyaromatic carboxylic acids of thetype contemplated herein involves the condensation of the corresponding alkylated hydroxyaromatic carboxylic acid wth sulfur or" sulfur halides, followed by the acylation of the hydroxyl group. In the above general procedure an alkali or alkaline earth metal salt of the alkyl-substituted hydroxyaromatic carboxylic acid (preferably the corresponding sodium phenate-sodium carboxylate), may be employed as the starting material in place of the free acid as will be more fully explained further on in connection with a specific example of this general method.

In the event sulfur dichloride (S012) is used in the'general procedure described above, the condensation product will be in the nature of a monosulflde (or a condensate or polymer thereof); sulfur monochloride (sicko wil yield the corresponding disulflde (or a conden ate .or polymer thereof) and, of-course, a mixture of sulfur halides may be employed to yield a. mixture of such sulfides. Elementary su fur may s employed as the condensation rea ent. but ths is not considered the most desirable procedure.

Sulfur derivatives of higher sulfur. content may be obtained by reacting a comp 'md having a disulflde linkage (obtained with sulfur monochloride) with sulfuror with a kali polysulfldes or with an alkyl tetrasulfide. Such higher sulfur derivatives may also be obtained by first reducing the disulfide to form an aryl mercaptan or thio-phenol of the alkylated hydroxyaromatic acid (or alkali metal carboxylate) and then reacting the thio-phenol with kyl ar'yl ethers may also be used in the formation sulfur dichloride (to form the trisulfide) or with sulfur monochloride (to form the tetrasulfide) of the alkylated hydroxyaromatic carboxylic acid (or alkali metal salt thereof), which can then be acylated to form the polysulfide of the corresponding acyloxyaromatic carboxylic acid as explained above.

The alkylated hydroxyaromatic carboxylic acid or alkali or alkaline earth metal salt thereof) used in the above general procedure in preparing the sulfides of the corresponding acylated derivatives may be obtained in various ways. For example, a hydroxyaromatic compound such as phenol or naphthol may first be alkylated to substitute part of the nuclear hydrogen with an alkyl group or groups preferably of suflicient size to impart oil-miscibility to the ultimate product. This alkylated hydroxyaromatic compound may then be converted to the corresponding hydroxyaromatic carboxyl c acid by a suitable carboxylation procedure. For example. the alkylated hydroxy-aromatic compound may be subjected to the Kolbe synthesis described in detail in my copending application Serial Number 206, 682, filed May 7,1938, to form an alkali or alkaline earth metal carboxylate salt of the alkylated hydroxyaromatic acid, which may be used. as the starting material in the above general procedure or, ifdesire'd, this salt maybe acidified to form the. corresponding carboxylic acid or converted to an alkali-phenate-alkali carboxylate (or the corresponding alkaline earth compound), either of which may also be employed as a starting material, as explained above.

The alkylation of the hydroxyaromatic com-. pound may be carried out in various ways. A

preferred procedure is to subject a hydroxyaromatic compound to a Friedel-Crafts condensa tion reaction with a halogenated aliphatic hydrocarbon, which for obtaining the preferred multifunctional addition agents for mineral oils,

of alkylated hydroxyaromatic compounds :by the Friedel-Crafts reaction, rearrangement of the alkyl or aralkyl ether radical taking place to give hydrous aluminum chloride as a catalyst. For

obtaining the preferred multifunctional addition agents for mineral oils the unsaturated hydrocarbons or aliphatic alcohols should be high molecular weight compounds containing at least twenty carbon atoms such, for example, as eicosylene, cerotene, melene, polymerized isobutylme, etc., or.myricyl alcohol, ceryl alcohol, etc. The Friedel-Crafts synthesis is preferred for obtaining the alkylated hydroxyaromatic compound, and as a source of the alkyl substituent preference is given to mixed high molecular weight hydrocarbons typified by those which characterize the heavier products of petroleum, such as heavy petroleum oils of the lubricant type, petrolatum and crystalline petroleum wax or other compounds which will result in relatively long chain aliphatic substituents. Special preference is given to petroleum wax of melting point not substantially less than about E, which is predominently characterized by aliphatic hydrocarbons having a molecular weight of about 350 and containing at least twenty carbon atoms.

Hydroxyaromatic compounds which may be used in the alkylation reaction-are: monoor poly-cyclic and monoor polyhydric hydroxyaromatic compounds which may or may not be I otherwise substituted, as hereinafter indicated. Specific examples of compounds which may be used in this reaction are: phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol, phenylethyl phenol, phe- ,no1 resins, methylhydroxydiphenyl, alpha and beta naphthol, xylyl naphthol, benzyl phenol, anthranol, phenyimethyl naphthol, phenanthrol, anisole, beta naphthyl methyl ether, chlorphenol, and the like. Preference in general is to the monohydroxy phenols otherwise unsubstituted, particular preference being given to phenol and alpha and beta naphthol.

Where it is desired to obtain a compound or condensation product in which the aryl nucleus contains in addition to, or instead of, residual hydrogen, a substituent of the type represented in the above general formula, it is pointed out that with the exception of substituents such as aralkyl, aryl, alkaryl, halogen, hydroxyl, and

aroxy, such groups are introduced after alkylatacids of non-metallic or acidic metalloid elements that may be used in the acylation reaction mentioned above are the following:

POCls, PSCls, B011, SiCh, PCls, PO15, as well as the corresponding bromides and iodides- Representative examples of the organic acid anhydrides or acyl halides which may be used for this purpose are the anhydrides or acyl halides of the following organic acids:

(1) Saturated aliphatic mono-carboxylic acids ranging from acetic to montanic acid.

.(2)- Unsaturated aliphatic mono-carboxylic' acids'such as acrylic, oleic, elaidic, crotonic, etc.

(3) Saturated aliphatic poly-carboxylic acids aliphatic acids with carboxyl in the side'chain such as phenylstearic, naphthyl stearic and V naphthyl polystearic acids.

'as halogen, cyano, nitro, and thio groups. The

general methods for introducing these groups into such nuclear substituents in the case of simpler compounds are well known to those skilled in the art and have also been found to be applicable here. V

In the event it is desired to produce a product which contains an alkoxy or aroxy group as a substituent on the aryl nucleus, it is preferable to use an aryl hydroxide containing such substituent and effect the alkylation with a high molecular weight unsaturated aliphatic hydrocarbon (such as eicosylene, cerotene, melene, etc.) or a higher alcohol (such as myricyl alcohol, ceryl alcohol, etc.) using H2804 as a catalyst. By this procedure the hydroxyaromatic ethercan be alkylated without substantial rearrangement taking place. dric phenols can be alkylated with higher alcohols or high molecular weight aliphatics or'by Friede -Crafts reaction, followed by substitution of one\ hydroxyl'hydrogen-with a low molecular weight alkyl .group, which substitution can be effected by treating the alkylated polyhydric pheol with an alkali alcoholate to substitute an OH group with alkali metal and then treating-with the desired alkyl halide whereby the substitution is effected.

when it is desired to obtain a nitro or amino substituent, the aryl hydroxide is alkylated or wax-substituted when free of such substituent. This is followed by nitration tointroduce the nitro group. The amino group can be obtained by reduction, of the nitro group.

As an altemative procedure, polyhy- (10) Substituted aromatic. mono and polycarboxylic acids, containing halogen, hydroxyl, amino, alkyl, aryl, aralkyl, keto, nitro or alkoxy in the nucleus, such as chlorbenzoic, salicylic, anthranilic, toluic, phenyl-benzoic, benzoylbenzoic', nitro-benzoic, and anisic acid.

(11) Non benzenoid cyclic mono and polycarboxylic acids such as abietic and camphoric acids, and heterocyclic carboxylic acids such as furoic acid.

Of the above organic acylating agents, those corresponding to-the saturated aliphatic and aromatic acids are preferred. In most cases, compounds which impart higher V. I. to mineral oils can be prepared by use of the dibasic acid chlorides because of the formation of more resinous products thereby..

To illustrate the procedure which may be followed in preparing the compositions contemplated by this invention, I will now describe the various steps which may be followed in synthesizing the monosulfide or the disulflde of the phosphite ester (acyl) of wax phenol carboxylic acid.

. By the term wax in this connection I mean, as previously indicated, a mixture of higher aliphatic radicals or groups corresponding to the higher aliphatic hydrocarbons which characterize petroleum wax, the resulting product being, therefore, a mixture of the sulfides (monoor di-) of the corresponding nuclear allwl-substituted phosphite esters of phenol carboxylic acid. The procedure to be followed in preparing other esters, other polysulfides and other condensation products such as selenides and tellurides, containing other alkyl substituents than those derived from petroleum wax and other aryl nuclei than that characterizingphenol will be obvious from the following description in the light of the foregoing. L The following description also illustrates the procedure which may be followed in making those Examples of acyl chlorides of theinorganic 76 compounds which are preferred for their multifunctional oil-improving properties. As will be apparent to those skilled in the art, compounds or compositions having a combined phenol content in excess of that necessary for oil-miscibility may be readily obtained by using a chlorinated wax having a chlorine content substantially higher than that given in the example below or by changing the ratio of the reactants (chlorwax and phenolic compound).

ALKYLATION or PHENOL proportions of chlorine is heated to a temperature varying from just above its melting point to not over 150 F., and 1 mol of phenol (hydroxybenacne) is admixed therewith. The mixture is heated to about 150 F., and a quantity of anhydrous aluminum chloride corresponding to about 3 per cent of the weight of the chlor-wax in the mixture is slowly added with active stirring.

The rate of addition of the aluminum chloride should be sufllciently slow to avoid violent roaming, and during such addition the temperature is preferablyheld at about 150 F.; afterthe aluminum chloride has been added, the temperature of the mixture may .be increased slowly to control the evolution of HCl gas to a temperature of from 250 F. to 300-350 F. If the emission of HCl gas has not ceased when the final temperature is reached, the mixture may be held at 350 F. for a short time to allow completion of the reaction, but to. avoid possible cracking of the wax the mixture should not be heated appreciably above 350 F., nor should it be held 'at that temperature for any extended length of time. Removal of non-alkylated material (pheol) can be eiIected generally by water-washing, but it is preferable to treat the water-washed product with super-heated steam, thereby insurin complete removal of the unreacted material and accomplishing the drying of the product in the same operation.

A wax-substituted phenol prepared according to the-above procedure in which a quantity of chlor-wax containing 3 atomic proportion of chlorine (16 per cent chlorine in the chlor-wax) is reacted with 1 molecular proportion of phenol, may for brevity herein be designated as waxphenol (3-16). Parenthetical expressions of the type (A-B) will be used hereinafter in connection with the alkylated hydroxyaromatic compounds to designate (A) the number of atomic proportions of chlorine in the chloraliphatic material reacted with one mol of hydroxyaromatic compound in the Friedel-Cratts reaction and (B) e P rcentage of chlorine in the chloraliphatic material. In the above example A=3 and B=16. Thesame designation will also apply to the sultides or the wax-substituted acylated hydroxyaromatic carboxyiic acids which constitute the ultimate product derived from the wax-phenol.

Canaomarron or Wax-Pruner.

In forming the carboxylic acid or the alkali metal carboxylate of a wax-phenol of the type obtained by the procedure described above, a preferred method involves, first, the substitution of the phenolic hydrogen with alkali metal, followed by carboxylation with CO2 gas. Because of the high viscosity of the mixtures it is advantageous to dilute the wax-phenol initially with from one to three parts of heavy mineral oil, in which case the finished product is a concentrated mineral oil blend. By the use of mineral oil diluent, wax phenols of higher phenol content can be used in the formation of products of this invention.v

The formation of a .wax-alkali-metal-phenate, for example, maybe carried out by diluting 500 parts by weight of wax-phenol obtained according to the foregoing procedure, with 1500 parts by weight of mineral oil of Saybolt viscosity of about 60 seconds at 210 F., and reacting with 16 parts by weight of metallic sodium (or equivalent amount of metallic potassium). The reaction mixture is heated at about 500 F. during a two-hour period with rapid stirring to produce finely divided alkali metal and thereby acceler. ate the reaction. Wax-substituted alkali metal phenates may also .be prepared by reacting the wax-phenol with an alcoholate of the alkali metal such as sodium butylate. For this purpose anhydrous aliphatic alcohols are usually the most suitable; and as an example, 500 parts by weight of wax-phenol (3-16) was reacted with 16 parts by weight sodium in the forms of ethyl or butyl sodium oxide :by heating the mixture to about 300 l t-during about a one-hour period and allowing the alcohol released in the reaction to distill oil.

The wax-sodium phenate obtained according to the foregoing procedures is then carboxylatcd.

' This carboxylation may be carried out in various ways, one effective procedure being to heat the wax-sodium phenate in mineral oil blend to a temperature of about 350 F. and introduce C0:

When completely carboxylated, the mixture loses at this temperature. The pressure is gradually raised to about 500 pounds per square inch to complete the reaction at this temperature during a one-hour period. The car-boiwlation can also be carried out at atmospheric pressure, a suitable procedure consisting of introducing a current of CO: into the wax-sodium phenate in mineral oil blend at a temperature of about 400 F., the carboxylation requiring about 10 hours, depending somewhat upon the rate of stirring of the mixture.

The product of this step is the sodium carboxylate salt of wax-substituted phenol carboxylic acid (3-16); or in case mineral oil is used. as diluent, it is a mineral oil solution .of such salt.

its gelatinous nature, changing to a fluid homogeneous product. In the absence of diluent, the

Y wax-sodium phenate is changed from a waxy product to a resilient, rubbery material.

This salt may be converted, if desired, to the corresponding carboxylic acid by neutralization with a mineral acid orit may be converted to a sodium phenate-carboxylate salt by reacting with an amount of sodium alcoholate containing sodium equivalent to the hydroxyl hydrogen of the phenol sodium carboxylate.

Foruumorr or was Sou-mas or m Pnosrnn's ESTER OI wAX-PHINOL CARIOXYLIO Acm E, which is followed by addition of a sulfur halide (monoor di-) or mixture of sulfur halides during about a /z-hour period. The mixture may then be held at this temperature for about one hour to complete the formation of the sulfide derivative. HCl is evolved in the reaction, resulting in fixation of the sulfur in the aryl nucleus. As regards the temperature of the reaction, it is to be understood that the reaction can be carried out at various temperatures from room temperature up to the boiling point of the solvent, but it is preferable for obtaining light-colored products that the temperature be not too high. The addition of the sulfur halide is controlledso as to prevent over-heating of the mixture by its heat of reaction. This mixture is then water-washed to remove dissolved hydrochloric acid, and the free phenol-carboxylic acid may be acylatedwith phosphorou trichloride as herein before indicated, or if desired, it may be acylated after conversion to its corresponding alkali can-boxylate salt.

Where the Kolbe synthesis has been employed as the carboxylation procedure, the wax-phenol carboxylic acid may convenientlybe obtained in the form of the alkali carboxylate oralkali metal phenate-alkali metal carboxylate salt. The sulfide derivatives can .be obtained therefrom by.

boxylate salt, with formation of the corresponding free wax-substituted hydroxyaromatic (pheml) carboxylic acid or the mono-sodium salt, re-

spectively, when one equivalent of sulfur chloride is reacted therewith, which may then be reacted with an acyl halide as previously explained.

When the alkali salt of the acid is reacted in the manner just described, solvents such as ,carbon disulfide and ethylene dichloride must be replaced with solvents such as alcohol, benzene, or chlorbenzene to avoid side reactions with the alkali derivative.

The following example illustrates a preferred method of preparing the phosphite-ester (acyl) of wax-phenol carboxylic acid disulfide which is one of the preferred oil-improving agents of the present invention. It is to be understood, however, that my invention is not limited to the details of this specific example which is given merely by way of illustration and from which, taken in connection with the explanations and descriptions given above, the various other procedures and methodswhich may be followed for making this same product and for making the various other products comprised by the present invention will be apparent to those skilled in the art.

Preparation of the phosphite ester (acid) of was:- phenol carbon/lie acid disulfide Reaction mixture:

I Parts by weight Sodium carboxylate salt of wax-phenol The mineral oil solution of the sodium salt of wax phenol carboxylic acid is diluted with an equal 'weight' of chlorbenzene and the sulfur monochloride added at about F. at a rate sufliciently slow to prevent an increase in temperature of the reaction mixture by the heat of reaction, the addition of the sulfur monochloride requiring about a half hour period. The phosphorous trichloride is then added at 100 F. Thereaction mixture is then heated to about 250 Ffiuntil the acylation reaction is substantially completed and water washed to remove the sodium chloride formed in the reaction and to hydrolize any acid chloride formed by reaction of PCI: with the carboxyl group. The reaction mixture is then steam treated at about 300 F. to remove all traces of volatile solvent. The steam vapor is then removed by applying vacuum or by running through the mineral oil blend of the product, while cooling, a current of nitrogen to obtain the finished product.

The product of the foregoing specific example is the disulfide of the phosphite ester (acyl) of wax-phenol carboxylic acid. It may also be termed the phosphite ester of wax-phenol carboxylic acid disulfide. The procedure to be fol lowed in obtaining the corresponding disulfides of esters (acyls) other than the phosphite ester will be readily apparent from the foregoing to those skilled in the artfas will also the variations in the procedure necessary to obtain the corresponding monosulflde and other polysulfides of acylated wax-phenol and of other acylated waxhy'droxyaromatic carboxylic acids.

The wax-substituted compositions of the presthesized all have been tested as additive agents for viscous mineral oils and have been found to be of multifunctional activity, improving the pour point and viscosity index and inhibiting oxidation of viscous mineral oil fractions. The following list (table) is illustrative of the various oil-miscible compositions of the present invention which have been prepared and tested to demonstrate their value as additive agentsfor viscous mineral oils.

Table Phosphite ester of wax-phenol carboxylic 1 acid disulfide Phosphite ester of wax-phenol carboxylic acid tetrasulfide 3-14) 'I'hiophosphate ester of wax-phenol carboxylic acid disulfide (3-16) Phthalyl ester of wax-phenol carboxylic acid' disulfide (3-16) This application is a continuation in part of my copending application Serial Number-330,533, filed April 19, 1940.

I claim:

'The phosphite ester of paraflln-wax-phenol carboxylic acid disulfide.

' ORLAND M. REIFF. 

